EP1059310B1 - Polymerisation von Alpha-Olefinen in Gegenwart von Übergangsmetallkatalysatoren basierend auf Pyridin oder Chinolin enthaltenden zweizähnigen Liganden - Google Patents

Polymerisation von Alpha-Olefinen in Gegenwart von Übergangsmetallkatalysatoren basierend auf Pyridin oder Chinolin enthaltenden zweizähnigen Liganden Download PDF

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EP1059310B1
EP1059310B1 EP00110565A EP00110565A EP1059310B1 EP 1059310 B1 EP1059310 B1 EP 1059310B1 EP 00110565 A EP00110565 A EP 00110565A EP 00110565 A EP00110565 A EP 00110565A EP 1059310 B1 EP1059310 B1 EP 1059310B1
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catalyst
polymerization
cyclopentadienyl
transition metal
titanium
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French (fr)
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EP1059310A2 (de
EP1059310A3 (de
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Sandor Nagy
Ramesh Krishnamurti
John A. Tyrell
Leonard V. Cribbs
Mary Cocoman
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Equistar Chemicals LP
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Equistar Chemicals LP
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Definitions

  • This invention relates to catalysts useful in polymerizing ⁇ -olefins.
  • it relates to the polymerization of ethylene using transition metal catalysts with bidentate ligands containing pyridine or quinoline moieties.
  • transition metal catalysts with bidentate ligands containing pyridine or quinoline moieties.
  • the compounds of the invention contain a titanium which forms a non-sigma bond to the nitrogen as well as a sigma bond to an oxygen atom which in turn is bond to the heterocyclic ring.
  • a Ziegler catalyst typically consists of a transition metal-containing compound and one or more organometallic compounds.
  • polyethylene has been made using Ziegler catalysts such as titanium trichloride and diethylaluminum chloride, or a mixture of titanium tetrachloride, vanadium oxytrichloride, and triethylaluminum. These catalysts are inexpensive but they have low activity and therefore musts be used at high concentrations.
  • the catalyst residue in the polymers produces a yellow or grey color and poor ultraviolet and long term stability, and chloride-containing residues can cause corrosion in polymer processing equipment.
  • Ziegler catalysts produce polymers having a broad molecular weight distribution, which is undesirable for some applications, such as injection molding. They are also poor at incorporating ⁇ -olefin co-monomers, making it difficult to control polymer density. Large quantities of excess co-monomer may be required to achieve a certain density and many higher ⁇ -olefins, such as 1-octene, can be incorporated at only very low levels, if at all.
  • a metallocene catalyst typically consists of a transition metal compound that has one or more cyclopentadienyl ring ligands. Metallocenes have low activities when used with organometallic compounds, such as aluminum alkyls, which are used with traditional Ziegler catalysts, but very high activities when used with aluminoxanes as cocatalysts. The activities are generally so high that catalyst residues need not be removed from the polymer. Furthermore, they produce polymers with high molecular weights and narrow molecular weight distributions They also incorporate ⁇ -olefin co-monomers well.
  • US-A-3 900 452 (see claim 1) describes a method for ⁇ -olefin copolymerization with at least one triene in the presence of various cocatalysts (claim 10) for the preparation of high molecular weight (claim 1) linear amorphous copolymers at 25°C (examples 21 and 22).
  • metallocene catalysts tend to produce lower molecular weight polymers.
  • they are useful for gas phase and slurry polymerizations of ethylene, which are conducted at about 80°C to about 95°C, but in general. they do not work well as temperatures are increased.
  • the polymerization of ethylene in solution at higher temperatures is desirable because it allows great flexibility for producing polymers over a wide range of molecular weights and densities as well as the use of a large variety of different co-monomers.
  • Solution polymerization permits the production of polymers that are useful in many different applications. For example, both high molecular weight, high density polyethylene (PE) film useful as a barrier film for food packaging and low density ethylene co-polymers with good toughness and high impact strength can be made.
  • PE high density polyethylene
  • the transition metal catalysts of this invention containing the bidentate pyridine based ligand have the general formula where Y is O, S, NR, each R is independently selected from hydrogen or C 1 to C 6 alkyl, each R' is independently selected from R, C 1 to C 6 alkoxy, C 6 to C 16 aryl, halogen, or ⁇ F, M is titanium, zirconium, or hafnium, each X is independently selected from halogen, C 1 to C 6 alkyl, C 1 to C 6 alkoxy, or L is X, cyclopentadienyl, C 1 to C 6 alkyl substituted cyclopentadienyl, indenyl, fluorenyl, or "m" is 0 to 4, and "n” is 1 to 4.
  • the Y group is preferably oxygen as those compounds are easier to make.
  • the R group is preferably methyl and "R'" is preferably hydrogen.
  • the L group is preferably halogen, most preferably chlorine, as those catalysts give superior properties and are easier to prepare.
  • the X group is preferably halogen, especially chlorine, and the M group is preferably titanium.
  • Preparation of the bidentate pyridine complexes is illustrated in the examples; but generally they can be prepared by reacting a substituted pyridine precursor having an acidic proton with a compound having the formula MX 3 L in the presence of an HX scavenger.
  • the reaction is stoichiometric and stoichiometric amounts of scavenger are preferred.
  • suitable scavengers include compounds that are more basic than the substituted pyridine, such as triethylamine, pyridine, sodium hydride, and butyl lithium. If the scavenger is a stronger base than the substituted pyridine one can make a salt of the substituted pyridine and begin with that.
  • An aprotic solvent such as tetrahydrofuran (THF), ether, toluene, or xylene, can be used at about 0.2 to about 20 wt% solids, and preferably at about 5 5o about 10 wt% solids.
  • THF tetrahydrofuran
  • ether ether
  • toluene or xylene
  • the reaction can occur at about -78°C to about room temperature. As the reaction proceeds a precipitate is formed and the product can be extracted with toluene, methylene chloride, diethyl ether, or a similar extractant.
  • the bidentate quinoline transition metal catalyst of this invention have the general formula where R, R', L, M, X, and "n" where previously defined.
  • the quinoline transition metal catalysts are made in a similar manner to the pyridine transition metal catalysts except that one begins with a substituted quinoline such as 8-hydroxy quinoline (also known as 8-quinolinol) instead of the substituted pyridine.
  • a substituted quinoline such as 8-hydroxy quinoline (also known as 8-quinolinol) instead of the substituted pyridine.
  • butyl lithium can be used in a solvent to make the lithium salt of 8-hydroxy quinoline, which can also be used as the starting material.
  • the catalyst is normally used in conjunction with an organometallic co-catalyst, it is preferable to dissolve the catalyst in a solvent in which the co-catalyst is also soluble.
  • a solvent in which the co-catalyst is also soluble.
  • MAO methylaluminoxane
  • PMAO polymethylaluminoxane
  • toluene, xylene, benzene, or ethylbenzene could be used as the solvent.
  • the preferred co-catalyst is MAO as it results in high activity and, a polymer having a narrower molecular weight distribution.
  • the mole ratio of the organometallic co-catalyst to catalyst when used in a polymerization is generally in the range 0.01:1 to 100,000:1, and preferably ranges from 1:1 to 10,000:1.
  • An alternative co-catalyst is an acid salt that contains a non-coordinating inert anion (see U.S. Patent No. 5,064,802).
  • the acid salt is generally a non-nucleophilic compound that consists of bulky ligands attached to a boron or aluminium atom, such as lithium tetrakis (pentafluorophenyl borate, lithium tetrakis(pentafluorophenyl)aluminate, anilinium tetrakis(pentafluorophenyl)borate, and mixtures thereof.
  • the anion which results when these compounds react with the catalyst is believed to be weakly coordinated to the metal-containing cation.
  • the mole ratio of acid salt to catalyst can range from about 0.01:1 to about 1000:1, but is preferably about 1:1 to 10 :1. While there is no limitation in the method of preparing an active catalyst system from the catalyst and the acid salt, preferably they are mixed in an inert solvent at temperatures in the range of about -78°C to about 150°C. They can also be mixed in the presence of monomer if desired.
  • the acid salt can be used in combination with the organometallic cocatalysts described earlier.
  • the catalyst and co-catalyst can be used in a support such as silica gel, alumina, silica, magnesia, or titania, but supports are not preferred as they may leave contaminants in the polymer. However, a support may be required, depending upon the process being utilized. For example, a support is generally needed in gas phase polymerization processes and slurry polymerization processes in order to control the particle size of the polymer being produced and in order to prevent fouling of the reactor walls. To use a support, the catalyst and co-catalyst are dissolved in the solvent and are precipitated onto the support material by, for example, evaporating the solvent. The co-catalyst can also be deposited on the support or it can be introduced into the reactor separately from the supported catalyst.
  • the catalyst is used in a conventional manner in the polymerization of olefinic hydrocarbon monomers. While unsaturated monomers, such as styrene, can be polymerized using the catalyst of this invention, it is particularly useful for polymerizing ⁇ -olefins such as propylene, 1-butene, 1-hexene, 1-octene, and especially ethylene.
  • the catalyst is also useful in a conventional manner for copolymerizing mixtures of unsaturated monomers such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, and the like; mixtures of ethylene and di-olefins such as 1,3-butadiene, 1,4-hexadiene, 1,5-hexadiene, and the like; and mixtures of ethylene and unsaturated comonomers such as norbornene, ethylidene norbornene, vinyl norbornene, norbornadiene, and the like.
  • unsaturated monomers such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, and the like
  • mixtures of ethylene and di-olefins such as 1,3-butadiene, 1,4-hexadiene, 1,5-hexadiene, and the like
  • mixtures of ethylene and unsaturated comonomers such as norbornene, e
  • the catalysts of this invention can be utilized in a variety of different polymerization processes. They can be utilized in a liquid phase polymerization process (slurry, solution, suspension, bulk phase, or a combination of these), in a high pressure fluid phase, or in a gas phase polymerization process. The processes can be used in series or as individual single processes.
  • the pressure in the polymerization reaction zones can range from about 15 psia to about 50,000 psia and the temperature can range from about -78°C to about 300°C.
  • Toluene slurries of lithium salts of various 8-quinolinol derivatives prepared using butyl lithium
  • the corresponding titanium or zirconium compound titanium or zirconium compound (titanium tetrachloride, zirconium tetrachloride, cyclopentadienyl titanium trichloride, or cyclopentadienyl zirconium trichloride) at -78°C and stirred overnight at room temperature.
  • the complexes were recovered from the reaction mixture by extraction with toluene or methylene chloride.
  • a toluene solution of catalyst was added to the reactor by nitrogen over pressure.
  • the reactor was maintained at isothermal conditions throughout the run.
  • Ethylene was admitted to the reactor and controlled at 150 psi with feed on demand via a pressure regulator. After the reactor temperature and pressure stabilized, the catalyst slurry was charged into the reactor and polymerization initiated. Ethylene flow was monitored via a Brooks mass flow meter.
  • Polymerization was terminated by venting the reactor and the polymer was recovered by filtration.
  • the polymer was stabilized by the addition of about 1000 ppm of butylated hydroxytoluene/hexane (BHT) and further devolatilized 2 hours at 80°C in a vacuum oven.
  • BHT butylated hydroxytoluene/hexane
  • Melt flow properties of the polymer were determined in accordance with ASTM D-1238. Polymer densities were measured on compression molded samples in a density gradient column in accordance with ASTM D-1505 85.
  • kg/gm/h is kilograms polymer produced per gram of catalyst per hour.
  • the melt index of the polymer was measured according to ASTM D-1238, Condition E and Condition F.
  • MI2 is the melt index measured with a 2.16 kg weight (Condition E) .
  • MI20 is the melt index measured with a 21.6 kg weight (Condition F).
  • MFR is the ratio of MI20 to MI2.
  • the polymer density was measured according to ASTM D-1505.
  • the molecular weight distribution of the polymer was measured using a Waters 150C gel permeation chromatograph at 135°C with 1,2,4-dichlorobenzene as the solvent. Both weight average molecular weight (Mw) and the ratio of Mw to Mn (number average molecular weight) are used to characterize the molecular weight distribution.
  • the catalysts of this invention gave good productivities and high molecular weight polymers, as evidenced by very low MI values, and Catalysts VI and VII did so even at higher temperatures (110°C).

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Claims (12)

  1. Verfahren zur Herstellung eines Poly-α-Olefins, umfassend das Polymerisieren eines α-Olefin-Monomers unter Verwendung eines Katalysatorsystems, das umfasst:
    (a) einen Katalysator der allgemeinen Formel
    Figure imgb0020
    wobei Y O, S, NR ist,
    Figure imgb0021
    jedes R unabhängig aus Wasserstoff oder C1 bis C6-Alkyl ausgewählt wird; M Titan, Zirconium oder Hafnium ist; jedes X unabhängig ausgewählt wird aus Halogen, C1 bis C6-Alkyl, C1 bis C6-Alkoxy oder
    Figure imgb0022
    L X, Cyclopentadienyl, C1 bis C6-Alkyl-substituiertes Cyclopentadienyl, Indenyl, Fluorenyl ist oder
    Figure imgb0023
    jedes R' unabhängig ausgewählt wird aus R, C1 bis C6-Alkoxy, C6 bis C16-Aryl, Halogen oder CF3; und
    "n" 1 bis 4 ist
    und (b) einen Cokatalysator, der ausgewählt wird aus der Gruppe, die aus Methylaluminoxan (MAO), Polymethylaluminoxan (PMAO) und sauren Salze von sich nicht koordinativ anlagernden inerten Anionen besteht.
  2. Verfahren nach Anspruch 1, wobei der Katalysator die allgemeine Formel hat:
    Figure imgb0024
  3. Verfahren nach Anspruch 2, wobei Y Sauerstoff und X Halogen ist.
  4. Verfahren nach Anspruch 2, wobei M Titan ist.
  5. Verfahren nach Anspruch 2, wobei M Zirconium ist.
  6. Verfahren nach Anspruch 5, wobei Y Sauerstoff und X Halogen ist.
  7. Verfahren nach Anspruch 6, wobei X Chlor ist.
  8. Verfahren nach Anspruch 7, wobei L Cyclopentadienyl ist.
  9. Verfahren nach Anspruch 8, wobei R' unabhängig ausgewählt wird aus der Gruppe, die aus Chlor, Methyl und Gemischen davon besteht.
  10. Verfahren nach Anspruch 1, wobei der Katalysator ausgewählt wird aus der Gruppe, die aus 8-Quinolinoxy-titantrichlorid, 8-(2-Methyl-5,7-dichloroquinolin)oxytitantrichlorid, (Cyclopentadienyl)-(8-quinolinoxy)zirconiumdichlorid, (Cyclopentadienyl)-[8-(2-methyl-5,7-dichloroquinolin) oxy]zirconiumdichlorid und Gemischen davon besteht.
  11. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Katalysatorsystem ein Trägerkatalysatorsystem ist.
  12. Verfahren nach einem der vorhergehenden Ansprüche, wobei das α-Olefin aus der Gruppe ausgewählt wird, die aus Ethylen und Propylen besteht.
EP00110565A 1995-04-17 1996-03-18 Polymerisation von Alpha-Olefinen in Gegenwart von Übergangsmetallkatalysatoren basierend auf Pyridin oder Chinolin enthaltenden zweizähnigen Liganden Expired - Lifetime EP1059310B1 (de)

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US6759493B1 (en) 2004-07-06
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WO1996033202A3 (en) 1996-11-28
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